JPH1062895A - Silver halide photographic sensitive material and image forming method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To enable lowering of minimum density substantially without impairing maximum density by incorporating a specified color developing agent and a color developing coupler and, further the coupler which performs a coupling reaction with the oxidation product of a color developing agent, but does not develop color so much as to contribute to image density. SOLUTION: At least one of hydrophilic colloidal layers formed on a support contains the color developing agent represented by the formula and the color developing coupler for forming a dye image, and further, a coupler in combination of this coupler for coupling with the oxidation product of the color developing agent but not so much to contribute substantially to image density. In the formula, Z is a carbamoyl or acyl or alkoxy- or aryloxy-carbonyl group; and Q is an atomic group necessary to form an unsaturated ring together with the C atom.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver halide photographic light-sensitive material containing a novel color developing agent, and more particularly to a silver halide photographic light-sensitive material having a clear image with less color turbidity and a good white background. About.

[0002]

2. Description of the Related Art In a color photographic light-sensitive material, after the material is exposed to light and color-developed, the oxidized color-developing agent reacts with a coupler to form a dye image. In this method, a color reproduction method based on a subtractive color method is used. To reproduce blue, green, and red, yellow, magenta, and cyan color images having complementary colors are formed. Color development is achieved by immersing the exposed color photographic material in an aqueous alkaline solution (developing solution) in which a color developing agent is dissolved. However, there is a problem that a color developing agent made of an aqueous alkaline solution is unstable and easily deteriorates with time, and it is necessary to frequently replenish the developing solution in order to maintain stable developing performance. In addition, the used developer containing the developing agent needs to be disposed of,
In conjunction with the frequent replenishment described above, processing of used developer discharged in large quantities is a major problem. Thus, there is a strong demand for achieving low replenishment and low discharge of the developer.

One of the effective means for solving the problem of low replenishment and low discharge of a developing solution is to incorporate an aromatic primary amine developing agent or its precursor into a hydrophilic colloid layer. Examples of suitable developing agents include, for example, U.S. Patent Nos. 803,783, 3,342,597, and 3,7.
19,492, 4,060,418, British Patent 1,069,061, West German Patent 1,159,758
No., JP-B-58-14,671 and No. 58-14,67
No. 2, JP-A-57-76,543 and JP-A-59-81,6
No. 43 and the like. However, color photographic light-sensitive materials containing these aromatic primary amine developing agents or their precursors have the disadvantage that sufficient color formation cannot be obtained during color development. Another effective means is a method of incorporating a sulfonylhydrazine type developing agent in a hydrophilic colloid. Examples of the developing agent which can be incorporated include, for example, European Patent Nos. 545,491A1 and 565.
165A1 and the like. But,
Even with the developing agents mentioned here, sufficient color formation has not yet been obtained at the time of color development, and the sulfonylhydrazine type developing agent has a problem that almost no color is formed when a 2-equivalent coupler is used. Compared with 4-equivalent couplers, 2-equivalent couplers have advantages such as reduction of coupler-derived stains and easy control of coupler activity. Accordingly, there has been a strong demand for a developing agent capable of obtaining a sufficient color at the time of development even when the coupler is incorporated, and capable of obtaining an image having good color development even when a 2-equivalent coupler is used. Further, there has been a problem that undesired color turbidity and white background density increase due to an increase in minimum density due to fog during development.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to provide a means for preventing color turbidity and an increase in the minimum density without adversely affecting the storability of a light-sensitive material. To provide a small photosensitive material.

[0005]

The object of the present invention has been attained by the following silver halide photosensitive material. That is, in at least one hydrophilic colloid layer provided on a support, a color image is formed by a coupling reaction with a color developing agent represented by the following general formula (I) and an oxidized form of the color developing agent. In the silver halide light-sensitive material containing a color developing coupler, a coupling reaction with an oxidized form of the color developing agent is further performed in combination with the above color developing coupler, but a color development substantially contributing to image density is obtained. It is characterized by containing a coupler (hereinafter, referred to as a non-colored coupler) which does not occur.

[0006]

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In the formula, Z represents a carbamoyl group, an acyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group, and Q represents an atomic group which forms an unsaturated ring with C.

[0008]

Next, the compound represented by formula (I) used in the present invention will be described in detail. In the general formula (I), Z represents a carbamoyl group, an acyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group. Of these, a carbamoyl group is preferable, and a carbamoyl group having one or more hydrogen atoms on a nitrogen atom is particularly preferable.

The carbamoyl group includes 1 to 50 carbon atoms.
Is preferred, and more preferably has 1 to 40 carbon atoms. Specific examples include carbamoyl, methylcarbamoyl, ethylcarbamoyl, n
-Propylcarbamoyl group, sec-butylcarbamoyl group, n-octylcarbamoyl group, cyclohexylcarbamoyl group, tert-butylcarbamoyl group, dodecylcarbamoyl group, 3-dodecyloxypropylcarbamoyl group, octadecylcarbamoyl group, 3- (2,
4-tert-pentylphenoxy) propylcarbamoyl group, 2-hexyldecylcarbamoyl group, phenylcarbamoyl group, 4-dodecyloxyphenylcarbamoyl group, 2-chloro-5-dodecyloxycarbonylphenylcarbamoyl group, naphthylcarbamoyl group, 3-
Pyridylcarbamoyl group, 3,5-bis-octyloxycarbonylphenylcarbamoyl group, 3,5-bis-
Examples include a tetradecyloxyphenylcarbamoyl group, a benzyloxycarbamoyl group, and a 2,5-dioxo-1-pyrrolidinylcarbamoyl group.

The acyl group is preferably an acyl group having 1 to 50 carbon atoms, more preferably 1 to 40 carbon atoms. Specific examples include formyl group, acetyl group, 2
-Methylpropanoyl group, cyclohexylcarbonyl group, n-octanoyl group, 2-hexyldecanoyl group,
A dodecanoyl group, a chloroacetyl group, a trifluoroacetyl group, a benzoyl group, a 4-dodecyloxybenzoyl group, a 2-hydroxymethylbenzoyl group, and a 3- (N-hydroxy-N-methylaminocarbonyl) propanoyl group.

The alkoxycarbonyl group and the aryloxycarbonyl group are preferably an alkoxycarbonyl group and an aryloxycarbonyl group having 2 to 50 carbon atoms, more preferably 2 to 40 carbon atoms. Specific examples include a methoxycarbonyl group, an ethoxycarbonyl group,
Isobutyloxycarbonyl group, cyclohexyloxycarbonyl group, dodecyloxycarbonyl group, benzyloxycarbonyl group, phenoxycarbonyl group, 4-octyloxyphenoxycarbonyl group, 2-hydroxymethylphenoxycarbonyl group, 4-dodecyloxyphenoxycarbonyl group and the like. Can be

Q represents an atomic group forming an unsaturated ring together with C. The unsaturated ring formed is preferably a 3- to 8-membered ring, more preferably a 5- to 6-membered ring. Examples thereof include a benzene ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a 1,2,4-triazine ring,
3,5-triazine ring, pyrrole ring, imidazole ring,
Pyrazole ring, 1,2,3-triazole ring, 1,2,
4-triazole ring, tetrazole ring, 1,3,4-thiadiazole ring, 1,2,4-thiadiazole ring, 1,
2,5-thiadiazole ring, 1,3,4-oxadiazole ring, 1,2,4-oxadiazole ring, 1,2,5
-Oxadiazole ring, thiazole ring, oxazole ring, isothiazole ring, isoxazole ring, thiophene ring and the like are preferable, and a condensed ring in which these rings are condensed with each other is also preferably used.

Further, these rings may have a substituent. Examples of the substituent include a linear or branched, chain or cyclic alkyl group having 1 to 50 carbon atoms (for example, trifluoromethyl). , Methyl, ethyl, propyl, heptafluoropropyl, isopropyl, butyl, t-butyl, t-pentyl, cyclopentyl, cyclohexyl,
Octyl, 2-ethylhexyl, dodecyl, etc.), linear or branched, chain or cyclic alkenyl group having 2 to 50 carbon atoms (eg, vinyl, 1-methylvinyl, cyclohexen-1-yl, etc.), total carbon number 2 to 2 50 alkynyl groups (eg, ethynyl, 1-propynyl, etc.), having 6 to 6 carbon atoms
50 aryl groups (eg, phenyl, naphthyl, etc.),
An acyloxy group having 1 to 50 carbon atoms (for example,

Acetoxy, tetradecanoyloxy, benzoyloxy, picolinoyloxy, etc.), having 1 to 1 carbon atoms
A carbamoyloxy group of 50 (for example, N, N-dimethylcarbamoyloxy, morpholinocarbonyloxy, etc.), a carbonamide group of 1 to 50 carbon atoms (for example, formamide, N-methylacetamide, acetamide,
N-methylformamide, benzamide, etc.), having 1 carbon atom
~ 50 sulfonamide groups (e.g., methanesulfonamide, dodecanesulfonamide, benzenesulfonamide, p-toluenesulfonamide, etc.);
Carbamoyl group (for example, N-methylcarbamoyl,
N, N-diethylcarbamoyl, N-methanesulfonylcarbamoyl and the like, a sulfamoyl group having 0 to 50 carbon atoms (for example, N-butylsulfamoyl, N, N-diethylsulfamoyl, N-methyl-N- (4 -Methoxyphenyl) sulfamoyl, decanoylsulfamoyl and the like, an alkoxy group having 1 to 50 carbon atoms (for example, methoxy, propoxy, isopropoxy, octyloxy, t
-Octyloxy, dodecyloxy, 2- (2,4-di-t-pentylphenoxy) ethoxy, etc.), having 6 to 6 carbon atoms.
50 aryloxy groups (eg, phenoxy, 4-methoxyphenoxy, naphthoxy, etc.), aryloxycarbonyl groups having 7 to 50 carbon atoms (eg, phenoxycarbonyl, naphthoxycarbonyl, etc.),

An alkoxycarbonyl group having 2 to 50 carbon atoms (eg, methoxycarbonyl, t-butoxycarbonyl, etc.), an N-acylsulfamoyl group having 1 to 50 carbon atoms (eg, N-tetradecanoylsulfamoyl, N-
Benzoylsulfamoyl, etc.), an alkylsulfonyl group having 1 to 50 carbon atoms (eg, methanesulfonyl, octylsulfonyl, 2-methoxyethylsulfonyl, 2-hexyldecylsulfonyl, etc.), and an arylsulfonyl group having 6 to 50 carbon atoms (eg, Benzenesulfonyl, p-toluenesulfonyl, 4-phenylsulfonylphenylsulfonyl, etc.), an alkoxycarbonylamino group having 2 to 50 carbon atoms (eg, ethoxycarbonylamino, etc.), and an aryloxycarbonylamino group having 7 to 50 carbon atoms (eg, Phenoxycarbonylamino, naphthoxycarbonylamino, etc.), an amino group having 0 to 50 carbon atoms (eg, amino, methylamino, diethylamino, diisopropylamino, anilino, morpholino, etc.), cyano group, nitro group, carboxyl A hydroxy group, a sulfo group, a mercapto group, an alkylsulfinyl group having 1 to 50 carbon atoms (eg, methanesulfinyl, octanesulfinyl and the like), an arylsulfinyl group having 6 to 50 carbon atoms (eg, benzenesulfinyl, 4-chlorophenylsulfinyl, p-toluenesulfinyl, etc.), having 1 to 5 carbon atoms
An alkylthio group of 0 (eg,

Methylthio, octylthio, cyclohexylthio, etc.), arylthio groups having 6 to 50 carbon atoms (eg, phenylthio, naphthylthio, 5-tetrazolylthio), and ureido groups having 1 to 50 carbon atoms (eg, 3-methylureido, 3 , 3-dimethylureide, 1,3-diphenylureide, etc.) and a heterocyclic group having 2 to 50 carbon atoms (for example, a heteroatom containing at least one or more of nitrogen, oxygen, sulfur and the like; Monocyclic or condensed ring, for example, 2-furyl, 2-pyranyl, 2
-Pyridyl, 2-thienyl, 2-imidazolyl, morpholino, 2-quinolyl, 2-benzimidazolyl, 2-benzothiazolyl, 2-benzoxazolyl, etc.), an acyl group having 1 to 50 carbon atoms (eg, acetyl, benzoyl,
Trifluoroacetyl, etc.), a sulfamoylamino group having 0 to 50 carbon atoms (eg, N-butylsulfamoylamino, N-phenylsulfamoylamino, etc.), a silyl group having 3 to 50 carbon atoms (eg, trimethylsilyl) , Dimethyl-t-butylsilyl, triphenylsilyl and the like), and a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom and the like). The above substituents may further have a substituent, and examples of the substituent include the substituents mentioned here.

The number of carbon atoms of the substituent is preferably 50 or less, more preferably 42 or less, and most preferably 30 or less. The substituent of the ring formed by Q and C described above is Hammett's substituent constant σ for all the substituents when the ring is formed only of carbon atoms (for example, a benzene ring, a naphthalene ring, and an anthracene ring). Value (when C has a relationship of 1, 2, 1, 4,...,
When there is a relationship of 1, 3, 1, 5,...
Is used. ) Is 0.8 or more and 4.0 or less, more preferably 1.2 or more and 3.5 or less, and most preferably 1.5 or more and 3.0 or less. The Hammett's substituent constants σp and σm are described, for example, by Naoki Inamoto, “Hammet Rule—Structure and Reactivity—” (Maruzen), “New Experimental Chemistry Lecture 14, Synthesis and Reaction of Organic Compounds V”, page 2605 (Japan). Chemical Society, Maruzen), Tadao Nakaya, "Explanation of theoretical organic chemistry" 2
17 pages (Tokyo Kagaku Doujin), Chemical Review (91
Vol.), Pages 165 to 195 (1991). Next, the color developing agent represented by the formula (I) will be specifically described, but the scope of the present invention is not limited to these specific examples.

[0018]

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[0019]

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[0020]

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[0021]

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[0022]

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[0023]

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[0024]

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[0025]

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[0026]

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Next, a general method for synthesizing the compound of the present invention will be described. Representative examples of the compounds used in the present invention are shown below. Other compounds can be synthesized in the same manner as in the following examples. Synthesis Example 1 Synthesis of Exemplified Compound (5) The compound was synthesized by the following synthetic route.

[0028]

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Synthesis of Compound (A-2) 1,2-Dichloro-4,5-dicyanobenzene (A-
1) (CAS Registry No. 139152-08-2) 5
3.1 g of N, N-dimethylformamide (DMF)
The resultant was dissolved in 1.1 liter, and 268 g of an aqueous solution of methyl mercaptan sodium salt (15%) was added dropwise at room temperature over 1 hour, and further stirred at 60 ° C. for 1 hour. The reaction was cooled to room temperature, poured into water and stirred for 30 minutes. The resulting white solid was collected by filtration, washed with water, and dried. Yield 46.5
g Yield: 78.1% Synthesis of compound (A-3) 41.1 g of compound (A-2) was suspended in 400 ml of acetic acid, and 89.3 g of potassium permanganate dissolved in 400 ml of water was added under water cooling. 1 hour. After standing at room temperature overnight, 2 liters of water and 2 liters of ethyl acetate were added, and the mixture was filtered through celite. The filtrate was separated, and the organic layer was washed with water, an aqueous solution of sodium hydrosulfite, an aqueous solution of sodium bicarbonate and brine, and then dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off, and a mixed solvent of ethyl acetate and hexane was added to the residue for crystallization to obtain 29.4 g of the compound (A-
3) was obtained as a white solid. Yield 55.0%

Synthesis of Compound (A-4) 29.4 g of Compound (A-3) was dissolved in 200 ml of dimethyl sulfoxide (DMSO), and 8.7 g of hydrazine monohydrate was added dropwise over 15 minutes while cooling with water. The mixture was stirred for 10 minutes under water cooling. The reaction solution was poured into water, and the generated yellow solid was collected by filtration, washed with water, and dried. Yield 17.4 g, Yield 7
0.9% Synthesis of Exemplified Compound (5) 11.8 g of Compound (A-4) was added to tetrahydrofuran 50
Then, 4.7 g of propyl isocyanate was added dropwise at room temperature over 30 minutes, and the mixture was further stirred for 1 hour. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with hydrochloric acid and brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off. The residue was crystallized from a mixed solvent of ethyl acetate-hexane (1:10) to obtain 14.5 g of Exemplified Compound (5) as a white solid. Yield 90.2
% Synthesis Example 2. Synthesis of Exemplified Compound (2) The compound was synthesized by the following synthesis route.

[0031]

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Synthesis of Compound (A-5) 84.7 g of Compound (A-1) and 89.95 g of potassium carbonate.
8 g was suspended in 600 ml of DMF, and 60.3 ml of 2-methylbutyl mercaptan was added dropwise at room temperature over 1 hour.
Further, the mixture was stirred at room temperature for 1 hour. The reaction mixture was poured into water and stirred for 10 minutes. The generated white solid was collected by filtration, washed with water, and dried. Yield 100.8 g, yield 88.5% Synthesis of compound (A-6) 98.0 g of compound (A-5) was obtained by adding 500 ml of acetic acid and 5 parts of water.
The resulting suspension was dissolved in 500 ml of water, and dropwise over 1 hour at room temperature. The mixture was further stirred at room temperature for 2 hours. 2 L of water and 2 L of ethyl acetate were added, and the mixture was filtered through celite.
The filtrate was separated, and the organic layer was washed with water, aqueous hydrosulfite solution, aqueous sodium bicarbonate and brine, and then dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off, and isopropyl alcohol was added to the residue for crystallization to give 53.2 g of the compound (A
-6) was obtained as a white solid. 48.4% yield

Synthesis of Compound (A-7) 50.5 g of Compound (A-6) was dissolved in 100 ml of DMSO, and 17.0 g of hydrazine monohydrate was added dropwise over 10 minutes under ice-cooling. Stirred for minutes. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous magnesium sulfate. After filtration, the solvent was distilled off, and the residue was purified by silica gel chromatography. Methylene chloride was used as eluent. Crystallization with ethyl acetate-hexane (1: 2) gave compound (A-
7) was obtained as a yellow solid. Yield 63.2% Synthesis of Compound (A-9) Compound (A-8) (CAS Registry No. 51461-11)
-1) 44.5 g was dissolved in 500 ml of ethyl acetate, and 500 ml of water in which 25 g of sodium bicarbonate was dissolved was added. To this solution, 16.4 g of phenyl chlorocarbonate was added dropwise at room temperature over 30 minutes, and the mixture was further stirred for 1 hour. Separate the reaction mixture,
The organic layer was washed with brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off to give Compound (A-9) 54.
0 g was obtained as a pale yellow oil. 95.6% yield

Synthesis of Exemplified Compound (2) 5.8 g of Compound (A-7), 11.3 of Compound (A-9)
g, DMAP (N, N-dimethylaminopyridine)
60 g was dissolved in 100 ml of acetonitrile and stirred at 60 ° C. for 3 hours. The reaction mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with aqueous sodium hydrogen carbonate, aqueous hydrochloric acid, and brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off. The residue was purified by silica gel column chromatography (eluent: ethyl acetate / hexane = 1/2) and crystallized from hexane to obtain 8.0 g of Exemplified Compound (2) as a white solid. Yield 52.4% Synthesis Example 3. Synthesis of Exemplified Compound (1) The compound was synthesized by the following synthetic route.

[0035]

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Synthesis of Exemplified Compound (1) Triphosgene (4.6 g) was dissolved in THF (100 ml) to give compound (A-10) (CAS Registry No. 61053-26-).
7) 13.6 g was added dropwise at room temperature over 10 minutes, and 18.7 ml of triethylamine was added dropwise at room temperature over 10 minutes. The mixture was reacted for 30 minutes to obtain a solution of the compound (A-11). To this reaction solution, 13.0 g of the compound (A-7) was added portionwise over 10 minutes at room temperature. After stirring for an additional hour, the mixture was poured into water and extracted with ethyl acetate. The organic layer was washed with aqueous sodium hydrogen carbonate, aqueous hydrochloric acid, and brine, dried over anhydrous magnesium sulfate, filtered, and the solvent was distilled off. The residue was purified by silica gel column chromatography, and ethyl acetate /
Crystallization was performed from a mixture of hexane = 1/10 to obtain Exemplified Compound (1) as a white solid. Yield 17.0 g, yield 6
1.3% Synthesis Example 4. Synthesis of Exemplified Compound (37) The compound was synthesized by the following synthetic route.

[0037]

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Compound (A-14) (European Patent No. 5454)
No. 91A1) 6.0 g and compound (A-9) 1
Synthesis was performed in the same manner as in Synthesis Example 2 using 4.98 g and 0.5 g of DMAP to obtain Exemplified Compound (37) as a white solid.
Yield 12.0 g, yield 65.3% Synthesis Example 5. Synthesis of Exemplified Compound (36) Compound (A-11) and compound (A-14) prepared in the same manner as in Synthesis Example 3 from 5.8 g of compound (A-10).
Using 3 g, it was synthesized in the same manner as in Synthesis Example 3 to obtain Exemplified Compound (36) as a white solid. Yield 6.7 g, Yield 61.5% Next, in the present invention, a color-forming coupler (hereinafter referred to as a color-forming coupler) which undergoes a coupling reaction with an oxidized form of a color developing agent represented by the general formula (I) to form a dye image. ). The color-forming coupler used in the present invention is preferably a 2-equivalent coupler in a system using a phenylenediamine-based color developing agent.
You may mix and use more than one kind. The color-forming coupler used in the present invention is preferably represented by the following formulas (1) to (12). These are generally active methylene, pyrazolone, pyrazoloazole, phenol, naphthol,
It is a compound generically referred to as pyrrolotriazole and is a compound known in the art.

[0039]

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[0040]

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[0041]

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Formulas (1) to (4) represent couplers referred to as active methylene couplers, wherein R ¹⁴ represents an optionally substituted acyl group, cyano group, nitro group, aryl group, A heterocyclic residue, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group, an alkylsulfonyl group, and an arylsulfonyl group. In the general formulas (1) to (3), R ¹⁵ is an alkyl group, an aryl group or a heterocyclic residue which may have a substituent. In the general formula (4), R ¹⁶ is an aryl group or a heterocyclic residue which may have a substituent. R ¹⁴ ,
Examples of the substituent which R ¹⁵ and R ¹⁶ may have include those described as examples of the substituent in Q in the above general formula (I).

In the general formulas (1) to (4), R ¹⁴ and R
¹⁵ , R ¹⁴ and R ¹⁶ may combine with each other to form a ring.
Formula (5) represents a coupler called a 5-pyrazolone-based coupler, wherein R ¹⁷ is an alkyl group, an aryl group,
Represents an acyl group or a carbamoyl group. R ¹⁸ represents a phenyl group or a phenyl group substituted with one or more halogen atoms, alkyl groups, cyano groups, alkoxy groups, alkoxycarbonyl groups, or acylamino groups. General formula (5)
Among the 5-pyrazolone-based couplers represented by, those in which R ¹⁷ is an aryl group or an acyl group and R ¹⁸ is a phenyl group substituted with one or more halogen atoms are preferable.

To describe these preferred groups in detail, R ¹⁷ is a phenyl group, a 2-chlorophenyl group, a 2-methoxyphenyl group, a 2-chloro-5-tetradecanamidophenyl group, a 2-chloro-5- (3-octadecenyl) group. -1-succinimide) phenyl group, 2-chloro-5-
An aryl group such as an octadecylsulfonamidophenyl group or a 2-chloro-5- [2- (4-hydroxy-3-t-butylphenoxy) tetradecanamido] phenyl group or an acetyl group, 2- (2,4-di-t) -Pentylphenoxy) butanoyl group, benzoyl group, 3- (2,
Acyl groups such as 4-di-t-amylphenoxyacetamido) benzoyl group, and these groups may further have a substituent, and these groups are organic groups linked by a carbon atom, an oxygen atom, a nitrogen atom or a sulfur atom. It is a substituent or a halogen atom.

R ¹⁸ is preferably a substituted phenyl group such as a 2,4,6-trichlorophenyl group, a 2,5-dichlorophenyl group and a 2-chlorophenyl group.

The general formula (6) represents a coupler called a pyrazoloazole coupler, wherein R ¹⁹ represents a hydrogen atom or a substituent. Q ³ represents a group of nonmetallic atoms necessary for forming a 5-membered azole ring containing 2 to 4 nitrogen atoms, and the azole ring may have a substituent (including a condensed ring).

Among the pyrazoloazole couplers represented by the general formula (6), in terms of the spectral absorption characteristics of the coloring dye,
Imidazo [1,2-b] pyrazoles described in U.S. Pat. No. 4,500,630;
No. 654, pyrazolo [1,5-b] -1,2,4
-Triazoles and pyrazolo [5,1-c] -1,2,4-triazoles described in U.S. Pat. No. 3,725,067 are preferred.

For details of the substituents on the azole ring represented by the substituents R ¹⁹ and Q ³ , see, for example, US Pat.
No. 0,654, column 2, line 41 to column 8, line 27. Preferably, JP-A-61-
No. 65245, a pyrazoloazole coupler having a branched alkyl group directly bonded to the 2, 3 or 6-position of the pyrazolotriazole group, and a sulfonamide group in the molecule described in JP-A-61-65245. A pyrazoloazole coupler having an alkoxyphenylsulfonamide ballast group described in JP-A-61-147254;
Pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position described in JP-A-209457 or JP-A-63-307453;
22279 is a pyrazolotriazole coupler having a carboxamide group in the molecule.

The general formulas (7) and (8) are couplers called a phenol coupler and a naphthol coupler, respectively, wherein R ²⁰ is a hydrogen atom or —CONR ²² R
_{^{23, -SO 2 NR 22 R 23}} , -NHCOR 22, -NHCO
NR ²² R ^23, represents a group selected from -NHSO ₂ NR ²² R ^23. R ²² and R ²³ represent a hydrogen atom or a substituent, and are preferably an alkyl, aryl or heterocycle. In the general formulas (7) and (8), R ²¹ represents a substituent, 1 represents an integer selected from 0 to 2, and m represents an integer selected from 0 to 4. When l and m are 2 or more, R ²¹ may be different from each other. Examples of the substituent of R ^{21 to} R ²³ include those described as examples of the substituent of Q in the general formula (I).

Preferred examples of the phenolic coupler represented by the general formula (7) include US Pat. No. 2,369,9.
No. 29, No. 2,801,171, No. 2,772
No. 162, No. 2,895,826, No. 3,77
2,002 and the like, 2-acylamino-5-alkylphenols, U.S. Pat. Nos. 2,772,162, 3,758,308, 4,126,396;
Nos. 4,334,011, 4,327,173
No. 3,329,729, West German Patent Publication No.
Nos. 2,166-9656, 2,5-diacylaminophenols, U.S. Pat. Nos. 3,446,622, 4,333,999, 4,451,559, and 4,427, No. 767, etc., and 2-phenylureido-5-acylaminophenols.

Preferred examples of the naphthol coupler represented by the general formula (8) include US Pat. No. 2,474,29.
No. 3, 4,052, 212 and 4,146, 3
No. 96, No. 4,282,233, No. 4,296,
No. 200, etc., and 2-carbamoyl-1-naphthols described in US Pat. No. 4,690,889 and the like.
-Carbamoyl-5-amido-1-naphthol type and the like.

Formulas (9) to (12) are pyrrolotriazo
A coupler called R ³², R³³, R³⁴Is water
Represents an atom or a substituent. R³², R³³, R³⁴Substituent
Is an example of the substituent for Q in the general formula (I) and
And those mentioned above. General formulas (9) to (12)
Preferred examples of the pyrrolotriazole coupler represented by
Are described in European Patent Nos. 488,248 A1 and 49
No. 1,197A1, No. 545,300.
R³², R³³At least one of which is an electron-withdrawing group
Ra.

In addition, couplers having structures such as condensed phenol, imidazole, pyrrole, 3-hydroxypyridine, active methylene, active methine, 5,5-condensed heterocycle, and 5,6-condensed heterocycle can be used.

US Pat. Nos. 4,327,173 and 4,564,586 as fused ring phenol couplers.
And the couplers described in JP-A Nos. 4,904,575 and the like can be used.

As the imidazole coupler, couplers described in US Pat. Nos. 4,818,672 and 5,051,347 can be used.

As the 3-hydroxypyridine coupler, couplers described in JP-A-1-315736 can be used.

Active methylene and active methine couplers are described in US Pat. Nos. 5,104,783 and 5,16.
2, 196, etc. can be used.

The 5,5-fused heterocyclic couplers include
Pyrrolopyrazole couplers described in U.S. Pat. No. 5,164,289, pyrroloimidazole couplers described in JP-A-4-174429, and the like can be used.

The 5,6-fused heterocyclic couplers include:
Pyrazolopyrimidine couplers described in U.S. Pat. No. 4,950,585, pyrrolotriazine couplers described in JP-A-4-204730, EP 556,70.
The couplers described in No. 0 can be used.

Y is a group which is bonded to a position where Cp causes a coupling reaction with an oxidized form of the color developing agent represented by the general formula (I), and is removed or removed in a dye formation process following the coupling reaction. . Examples of Y include a heterocyclic group (a saturated or unsaturated 5- to 7-membered monocyclic or condensed ring containing at least one heteroatom such as nitrogen, oxygen, sulfur, etc.) Linked by an existing heteroatom, such as succinimide, maleimide, phthalimide, diglycolimide, pyrrole, pyrazole, imidazole, 1,2,4-triazole, tetrazole, indole, benzopyrazole,
Benzimidazole, benzotriazole, imidazoline-2,4-dione, oxazolidine-2,4-dione, thiazolidine-2,4-dione, imidazolidin-
2-one, oxazolin-2-one, thiazoline-2-
ON, benzimidazolin-2-one, benzoxazolin-2-one, benzothiazolin-2-one, 2-pyrrolin-5-one, 2-imidazolin-5-one, indoline-2,3-dione, 2,6 -Dioxypurine, parabanic acid, 1,2,4-triazolidine-3,5-dione, 2-pyridone, 4-pyridone, 2-pyrimidone, 6
-Pyridazone, 2-pyrazone, 2-amino-1,3,4
-Thiazolidine, 2-imino-1,3,4-thiazolidine-4-one and the like), a halogen atom (for example, a chlorine atom,
A bromine atom), an aryloxy group (for example, phenoxy,
1-naphthoxy or the like), a heterocyclic oxy group (for example, pyridyloxy, pyrazolyloxy or the like), an acyloxy group (for example, acetoxy, benzoyloxy or the like), an alkoxy group (for example, methoxy, dodecyloxy or the like), a carbamoyloxy group (for example, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, etc.), aryloxycarbonyloxy group (eg, phenoxycarbonyloxy, etc.), alkoxycarbonyloxy group (eg, methoxycarbonyloxy, ethoxycarbonyloxy, etc.), arylthio group (eg, Phenylthio,
Naphthylthio, etc.), a heterocyclic thio group (eg, tetrazolylthio, 1,3,4-thiadiazolylthio, 1,3,
4-oxadiazolylthio, benzimidazolylthio, etc.), alkylthio group (eg, methylthio, octylthio, hexadecylthio, etc.), alkylsulfonyloxy group (eg, methanesulfonyloxy, etc.), arylsulfonyloxy group (eg, benzenesulfonyloxy, Toluenesulfonyloxy, etc.), carbonamide group (eg, acetamide, trifluoroacetamide, etc.),
Sulfonamide group (eg, methanesulfonamide, benzenesulfonamide, etc.), alkylsulfonyl group (eg, methanesulfonyl, etc.), arylsulfonyl group (eg, benzenesulfonyl, etc.), alkylsulfinyl group (eg, methanesulfinyl, etc.), aryl And a carbamoylamino group (for example, N-methylcarbamoylamino and the like). As a preferable bonding mode with Cp as Y, it is preferable to bond to Cp at an oxygen atom, a nitrogen atom, a sulfur atom, a phosphorus atom, a selenium atom, and a halogen atom (a fluorine atom, a chlorine atom, and a bromine atom) present in Y. , More preferably an oxygen atom, a sulfur atom,
A nitrogen atom and a halogen atom are most preferred, and an oxygen atom, a sulfur atom and a halogen atom are most preferred. Preferred specific examples of Y are a halogen atom, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an aryloxycarbonyloxy group, an alkoxycarbonyloxy group, a carbamoyloxy group, an arylthio group, and a heterocyclic thio group. Represents a halogen atom, an aryloxy group, a heterocyclic oxy group, an acyloxy group, an aryloxycarbonyloxy group, an alkoxycarbonyloxy group, or a carbamoyloxy group.

Y may be substituted by a substituent,
Examples of the substituent for Y are the same as those described for the substituent for Q in formula (I).

As for the color-forming coupler used in one layer, Cp and Y in the general formulas (1) to (12) may be used in combination of two or more different types.

In the present invention, in addition to the above-mentioned couplers for coloring,
West German Patent Nos. 3,819,051A and 3,823,
049, U.S. Pat. Nos. 4,840,883 and 5,
Nos. 024,930, 5,051,347 and 4,481,268, and EP 304,856 A2.
No. 329,036 and No. 354,549A2
No. 374, 781A2 and No. 379, 110A
No. 2, 386,930A1, JP-A-63-141
No. 055, No. 64-32260, No. 64-32261
JP-A-2-29747, JP-A-2-44340,
2-110555, 3-7938, 3-16
No. 0440, No. 3-172839, No. 4-17244
No. 7, 4-179949, 4-182645,
4-184337, 4-188138, 4-
Nos. 188139, 4-194847, 4-204
No. 532, No. 4-204731, No. 4-204732
Color-forming couplers described in Nos. 1 and 2 can also be used. Specific examples of the color-forming coupler used in the present invention will be listed, but the scope of the present invention is not limited to these specific examples.

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Next, a non-color-forming coupler used in combination with a color-forming coupler in the present invention will be described. The non-colored coupler in the present invention is preferably an unsubstituted active site coupler, or may be added to the same layer as the color-forming coupler,
It may be added to the layer adjacent to the color-forming coupler, but is preferably added to the same layer. In the present invention, the coupling reaction rate of the unsubstituted coupler at the active position with the oxidized form of the color developing agent represented by the general formula (I) is determined by the maximum rate of the color forming coupler existing in the same photosensitive layer or an adjacent layer thereof. Preferably has a relative speed of at least 0.1 times, more preferably at least 1.0 times,
It is more preferably at least 5.0 times, and most preferably at least 10.0 times. The value of the ratio of the coupling reaction rates is preferably as large as possible. There is no particular upper limit, but the upper limit is about 10 ⁸ or less. The coupling reaction rate is a value measured under a condition of pH 11 in a system of THF / water (volume ratio: 6: 4).

As the unsubstituted coupler having an active site used in the present invention, the couplers described for the color-forming coupler, in which Y is replaced by hydrogen, can be used. Further, since the unsubstituted coupler at the active position does not contribute to the image density, the same skeleton as the color-forming coupler may be used, or a different skeleton may be used.
One kind may be used, or two or more kinds may be used. Specific examples of the couplers having an unsubstituted active site used in the present invention are specifically described below, but the scope of the present invention is not limited thereto.

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The amount of the color-forming coupler used in the present invention depends on the molar extinction coefficient (ε) of the dye to be formed. Ε of the resulting dye is 5,000 to 50,000
In the case of a coupler of about 0, the coating amount is 0.001 to 1
About 00 mmol / m ² , preferably 0.01 to 10 mmol / m ² , more preferably 0.05 to 5 mmol / m ²
The degree is appropriate. The addition amount of the unsubstituted coupler used in the present invention is 0.000 to the color-forming coupler.
It is about 1 to 10 times, preferably 0.001 to 5 times, more preferably 0.01 to 1 time, and still more preferably 0.02 to 0.5 times.

The amount of the color developing agent represented by the general formula (I) of the present invention may be in a molar ratio of 0.1 to the total amount of the color-forming coupler and the non-color-forming coupler used in combination with each color developing agent. 01 to 100 times, preferably 0.1 to 10 times
Times, more preferably 0.2 to 5 times.

In the present invention, an auxiliary developing agent can be preferably used. Here, the auxiliary developing agent means a substance having an action of promoting the transfer of electrons from the color developing agent to the silver halide in the development process of silver halide development, and the auxiliary developing agent in the present invention is preferably a compound of the general formula The compound is an electron-emitting compound represented by (B-1) or the general formula (B-2), which conforms to the Kendall-Peltz rule. Among them, those represented by (B-1) are particularly preferred.

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In the general formulas (B-1) and (B-2),
R ^{51 to} R ⁵⁴ represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, or a heterocyclic group.

R ^{55 to} R ⁵⁹ are a hydrogen atom, a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, a heterocyclic group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, a heterocyclic oxy group. Group, silyloxy group, acyloxy group, amino group, anilino group, heterocyclic amino group, alkylthio group, arylthio group, heterocyclic thio group, silyl group, hydroxyl group,
Nitro group, alkoxycarbonyloxy group, cycloalkyloxycarbonyloxy group, aryloxycarbonyloxy group, carbamoyloxy group, sulfamoyloxy group, alkanesulfonyloxy group, arenesulfonyloxy group, acyl group, alkoxycarbonyl group,
Cycloalkyloxycarbonyl group, aryloxycarbonyl group, carbamoyl group, carbonamide group, ureido group, imide group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfonamide group,
Represents a sulfamoylamino group, an alkylsulfinyl group, an arenesulfinyl group, an alkanesulfonyl group, an arenesulfonyl group, a sulfamoyl group, a sulfo group, a phosphinoyl group, and a phosphinoylamino group.

Q represents an integer of 0 to 5, and when q is 2 or more, R ⁵⁵ may be different from each other. R ⁶⁰ represents an alkyl group or an aryl group.

Specific examples of the compound represented by formula (B-1) or (B-2) are shown below, but the auxiliary developing agent used in the present invention is not limited to these specific examples.

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In the present invention, a blocked photographic reagent which releases a photographically useful group upon processing as represented by the general formula (A) can be used. General formula (A) A- (L) n-PUG (1) A represents a block group in which a bond with (L) n-PUG (1) is cleaved during development processing, and L is L in general formula (A).
Represents a linking group in which the bond on the right side of L is cleaved after the bond on the left side of L is cleaved, n represents an integer of 0 to 3, and PUG (1)
Represents a photographically useful group.

The group represented by formula (A) will be described below. As the blocking group represented by A, the following known ones can be applied. That is, JP-B-48-9968, JP-A-52-8828, and 57-88.
No. 82834, U.S. Pat. No. 3,311,476, and Japanese Patent Publication No. 47-44805 (U.S. Pat.
No. 617) and the like, and a blocking group such as an acyl group or a sulfonyl group, and JP-B-55-17369 (U.S. Pat. No. 3,888,677), and JP-B-55-9696 (U.S. Pat. No. 830), No. 55-34927 (U.S. Pat. No. 4,009,029), and JP-A-56-7.
No. 7842 (U.S. Pat. No. 4,307,175) and No. 5
No. 9-105640, JP-A-59-105641, and JP-A-59-105542, and a blocking group utilizing a reverse Michael reaction.
Nos. 3,674,478 and 3,932.
480, 3,993,661, JP-A-57-13
Nos. 5944 and 57-135945 (U.S. Pat.
420,554), 57-136640, 61
196239, 61-196240 (U.S. Pat. No. 4,702,999), 61-185743,
No. 61-124941 (U.S. Pat. No. 4,639,40)
No. 8) and a block group utilizing formation of quinone methide or a compound similar to quinone methide by intramolecular electron transfer described in JP-A-2-280140 and the like;

US Pat. Nos. 4,358,525;
No. 330,617, JP-A-55-53330 (U.S. Pat. No. 4,310,612), and JP-A-59-121328.
Nos. 59-218439 and 63-3185
No. 55 (European Patent Publication No. 0295729), a blocking group utilizing an intramolecular nucleophilic substitution reaction, and JP-A-57-76541 (U.S. Pat. No. 4,335,20).
No. 0) and No. 57-135949 (U.S. Pat.
No. 0,752), No. 57-179842, No. 59-1
Nos. 37945, 59-140445 and 59-21
No. 9741, No. 59-202059, No. 60-410
No. 34 (U.S. Pat. No. 4,618,563),
No. 59945 (U.S. Pat. No. 4,888,268) and No. 62-65039 (U.S. Pat. No. 4,772,537).
No. 62-80647, JP-A-3-236047.
Groups utilizing ring opening of a 5- or 6-membered ring described in JP-A-5-238445 and JP-A-3-238445.
No. 9-201057 (U.S. Pat. No. 4,518,685)
No. 61-95346 (U.S. Pat.
No. 885) and No. 61-95347 (U.S. Pat.
No. 92,811), JP-A-64-7035, JP-A-6-7035
4-42650 (U.S. Pat. No. 5,066,573)
No.), JP-A-1-245255 and 2-207249.
No. 2,235,055 (U.S. Pat. No. 5,118,5)
No. 96) and 4-186344 and the like, a blocking group utilizing the addition reaction of a nucleophile to a conjugated unsaturated bond,

JP-A-59-93442 and JP-A-61-32
Nos. 839 and 62-163051 and 5-3
No. 7299 and the like, a blocking group utilizing a β-elimination reaction, a blocking group utilizing a nucleophilic substitution reaction of diarylmethanes described in JP-A-61-188540, No. 187850, a block group utilizing the Rossen rearrangement reaction.
Nos. 80646, 62-144163 and 62-
No. 147457, a block group utilizing the reaction of an N-acyl compound of thiazolidine-2-thione with an amine, JP-A-2-296240 (U.S. Pat.
No. 19,492), No. 4-177243, No. 4-17
No. 7244, No. 4-177245, No. 4-177724
No. 6, 4-177247, 4-177248,
4-177249, 4-179948, 4-
184337, 4-184338, WO92 / 21064, JP-A-4-330438, WO93 / 03419 and JP-A-5-4581.
JP-A-3-236047 and JP-A-3-238445, a blocking group having two electrophilic groups and reacting with a dinucleophile described in JP-A No. 6-360.

In the compound represented by formula (A), L
The group represented by may be any linking group capable of cleaving (L) _n-1 -PUG (1) after leaving from the group represented by A during development processing. . For example, U.S. Patent Nos. 4,146,396 and 4,652,51
No. 6,4,698,297, a group utilizing cleavage of a hemiacetyl tar ring, US Pat.
48,962, 4,847,185 or 4,857,440, a timing group for causing an intramolecular nucleophilic substitution reaction, US Pat. No. 4,409,3.
Utilizing a timing group for causing a cleavage reaction by utilizing an electron transfer reaction described in No. 23 or 4,421,845, and utilizing a hydrolysis reaction of imino ketal described in US Pat. No. 4,546,073. To cause a cleavage reaction, a group to cause a cleavage reaction by utilizing an ester hydrolysis reaction described in West German Patent Application No. 2,626,317, or a sulfite ion described in European Patent No. 0572844. And a group that causes a cleavage reaction by utilizing the reaction with Next, PUG in the general formula (A)
(1) will be described. PUG in general formula (A)
(1) represents a photographically useful group such as an antifoggant or a photographic dye. In the present invention, the compound represented by the general formula (B-1)
The auxiliary developing agent represented by (B-2) is particularly preferably used for PUG (1). General formulas (B-1), (B
The auxiliary developing agent represented by -2) is a PUG of the general formula (A)
In the case corresponding to (1), the bonding position is an oxygen atom or a nitrogen atom of the auxiliary developing agent.

The light-sensitive material of the present invention basically has a light-sensitive silver halide, a color developing agent, a coupler and a binder on a support, and further contains, if necessary, an organic metal salt oxidizing agent. Can be done. These components are often added to the same layer (a photosensitive layer or a non-photosensitive layer), but can be added separately to another layer as long as they can react. Hydrophobic additives such as couplers and color developing agents used in the present invention are described in U.S. Pat. No. 2,322,027.
It can be introduced into the layer of the light-sensitive material by a known method such as the method described in the above. In this case, U.S. Pat.
No. 55,470, No. 4,536,466, No. 4,
No. 536,467, No. 4,587,206, No. 4,555,476, No. 4,599,296, and Japanese Patent Publication No. 3-62256 require a high boiling point organic solvent. Can be used in combination with a low-boiling organic solvent having a boiling point of 50 to 160 ° C. depending on the solvent. Further, two or more of these couplers, color developing agents (diffusion-resistant reducing agents), high-boiling organic solvents and the like can be used in combination. The amount of the high boiling organic solvent is 10 to 1 g of the color image forming compound used.
g or less 0 or more, preferably 5 g or less, more preferably 1 or less.
g to 0.1 g. In addition, 1 to 1 g of binder
cc or less, more preferably 0.5 cc or less, especially 0.3 cc or less and 0 or more is suitable. Also, a dispersion method using a polymer described in JP-B-51-39853 and JP-A-51-59943, JP-A-62-30242 and JP-A-63-27 are disclosed.
No. 1339 can be used. When the hydrophobic additive is a compound substantially insoluble in water, it can be dispersed and contained as fine particles in a binder in addition to the above method. When dispersing the hydrophobic compound in the hydrophilic colloid, various surfactants can be used. For example, JP
The surfactants described in the RD magazine shown in pages (37) to (38) of JP-A-157636 and the following list can be used. In the light-sensitive material of the present invention, a compound for stabilizing an image simultaneously with activation of development can be used. Specific compounds preferably used are described in U.S. Pat. No. 4,500,626, columns 51-52.

In order to obtain a wide range of colors on the chromaticity diagram using the three primary colors of yellow, magenta and cyan, at least three silver halide emulsion layers having photosensitivity in different spectral regions are combined. Used. For example, there are a combination of three layers of a blue sensitive layer, a green sensitive layer, and a red sensitive layer, a combination of a green sensitive layer, a red sensitive layer, and an infrared sensitive layer. Each photosensitive layer can adopt various arrangement orders known for ordinary color photosensitive materials. Each of these photosensitive layers may be divided into two or more layers as necessary.

The photosensitive material can be provided with various auxiliary layers such as a protective layer, an undercoat layer, an intermediate layer, an antihalation layer, and a back layer. Further, various filter dyes can be added to improve color separation.

The silver halide emulsion which can be used in the present invention is:
Any of silver chloride, silver bromide, silver iodobromide, silver chlorobromide, silver chloroiodide, and silver chloroiodobromide may be used. The silver halide emulsion used in the present invention may be a surface latent image type emulsion or an internal latent image type emulsion. The internal latent image type emulsion is used as a direct reversal emulsion in combination with a nucleating agent or light fogging. Also,
It may be a so-called core-shell emulsion in which the inside of the grain and the surface layer of the grain have different phases, or silver halides having different compositions may be joined by epitaxial joining. The silver halide emulsion may be monodispersed or polydispersed, and a method of adjusting the gradation by mixing monodispersed emulsions as described in JP-A-1-167,743 and JP-A-4-223,643 is preferably used. . The particle size is preferably from 0.1 to 2 μm, particularly preferably from 0.2 to 1.5 μm. The crystal habits of silver halide grains include those having regular crystals such as cubic, octahedral, and tetrahedral, those having irregular crystal systems such as spheroids and high aspect ratio tabular, and those having twin planes. It may be one having such a crystal defect, or a composite system thereof, or any other. Specifically, US Pat. No. 4,500,626
No. 50, column 4,628,021, Research Disclosure Magazine (hereinafter abbreviated as RD) No. 17,0
29 (1978), No. 17, 643 (December, 1978), pp. 22-23, No. 18, 716 (1979).
Nov., 648, p. 307, 105 (198)
Nov. 9, pp. 863-865, JP-A-62-253,
No. 159, No. 64-13,546, JP-A-2-23
No. 6,546, No. 3-110, 555, and Grafkid, "Physics and Chemistry of Photography", published by Paul Montell (P.
Glafkides, Chemieet Phisique Photographique, Paul
Montel, 1967), Duffin's "Photoemulsion Chemistry", published by Focal Press (GFDuffin, Photographic Emul).
sion Chemistry, Focal Press, 1966), "Manufacture and coating of photographic emulsions" by Zerikman et al., published by Focal Press (VL Zelikman et al., Making and Coating Phot).
For example, any of silver halide emulsions prepared by the method described in, for example, photographic emulsions, Focal Press, 1964) can be used.

The use of the above tabular grains has advantages such as an increase in covering power and an increase in the color sensitization efficiency of a sensitizing dye, and is described in detail in US Pat. No. 4,434,226. I have. The average aspect ratio of 80% or more of the total projected area of the grains is desirably 1 or more and less than 100. It is more preferably 2 or more and less than 20 and particularly preferably 3 or more and less than 10. As the shape of the average particle, a triangle, a hexagon, a circle, or the like can be selected. A regular hexagon having approximately equal six sides as described in U.S. Pat. No. 4,798,354 is a preferred form. The equivalent circle diameter of the projected area is often used as the average particle size. However, particles having an average diameter of 0.6 μm or less as described in US Pat. preferable. Also, U.S. Pat.
Emulsions having a narrow grain size distribution as described in US Pat. No. 5,617 are also preferred. It is preferable to limit the grain thickness of the tabular grains to 0.5 μm or less, more preferably 0.3 μm or less, in order to increase sharpness. Further, an emulsion having a highly uniform thickness having a variation coefficient of grain thickness of 30% or less is also preferable. Further, particles described in JP-A-63-163451, in which the thickness of the particles and the distance between twin planes are specified, are also preferable. In the case of tabular grains, dislocation lines can be observed with a transmission electron microscope. It is preferable to select a particle containing no dislocation line, a particle containing several dislocations, or a particle containing many dislocations according to the purpose. Also, it is possible to select dislocations introduced linearly or distorted dislocations in a specific direction of the crystal orientation of the grains, to introduce them throughout the grains, or to introduce them only to a specific portion of the grains, For example, dislocations can be introduced only in the fringe portion of the particles. Introduction of dislocation lines is preferable not only in the case of tabular grains, but also in the case of irregular grains typified by normal crystal grains or potato grains. Also in this case, it is a preferable embodiment to limit to a specific portion such as a vertex or a ridge of the particle.

The photosensitive silver halide emulsion used in the present invention may contain heavy metals such as iridium, rhodium, platinum, cadmium, zinc, thallium, lead, iron, osmium and chromium for various purposes. These compounds may be used alone or in combination of two or more. In addition, these compounds can be added as salts such as chlorides, bromides, and cyanides, as well as various complex salts. The amount of addition depends on the purpose of use, but is generally about 10 ^-9 to 10 ^-3 mol per mol of silver halide.
Also, when it is contained, it may be uniformly introduced into the particles,
Further, it may be localized inside or on the surface of the particle. Specifically, Japanese Patent Application Laid-Open Nos. 2-236542 and 1-11663
No. 7, JP-A-5-181246 and the like are preferably used.

The light-sensitive silver halide emulsion is usually a chemically sensitized silver halide emulsion. The chemical sensitization of the photosensitive silver halide emulsion of the present invention includes known sulfur sensitization, selenium sensitization, chalcogen sensitization such as tellurium sensitization, gold, platinum, and noble metal sensitization using palladium. Methods and reduction sensitization methods can be used alone or in combination (for example, JP-A-3-110,555, JP-A-5-24).
1267). These chemical sensitizations can be carried out in the presence of a nitrogen-containing heterocyclic compound (Japanese Patent Application Laid-Open No. 62-25 / 1987).
3,159). Further, an antifoggant described later can be added after the completion of the chemical sensitization. More specifically,
-45,833 and JP-A-62-40,446. The pH at the time of chemical sensitization is preferably 5.3 to 10.5, more preferably 5.5 to 8.5.
And the pAg is preferably 6.0 to 10.5, more preferably 6.8 to 9.0. The coating amount of the photosensitive silver halide emulsion used in the present invention is in the range of 1 mg to 10 g / m ² in terms of silver.

In order to impart green, red and infrared sensitivity to the photosensitive silver halide used in the present invention, the photosensitive silver halide emulsion is spectrally sensitized with a methine dye or the like. . If necessary, the blue-sensitive emulsion may be subjected to spectral sensitization in the blue region. Dyes used include cyanine dyes, merocyanine dyes, complex cyanine dyes, complex merocyanine dyes, holopolar cyanine dyes, hemicyanine dyes, styryl dyes, and hemioxonol dyes. Specifically, U.S. Pat.
Sensitizing dyes described in JP-A-617,257, JP-A-59-180,550, JP-A-64-13,546, JP-A-5-45,828 and JP-A-5-45,834. These sensitizing dyes may be used alone, or a combination thereof may be used. The combination of sensitizing dyes is often used particularly for the purpose of supersensitization or wavelength adjustment of spectral sensitivity. Along with the sensitizing dye, a dye which does not itself have a spectral sensitizing effect or a compound which does not substantially absorb visible light and exhibits supersensitization may be contained in the emulsion (for example, US Pat. 615,641, JP-A-63-23145, etc.). These sensitizing dyes may be added to the emulsion at or before or after chemical ripening, or according to U.S. Pat. Nos. 4,183,756 and 4,225,666 before and after nucleation of silver halide grains. Good. These sensitizing dyes and supersensitizers may be added as a solution of an organic solvent such as methanol, a dispersion of gelatin or the like, or a solution of a surfactant. The amount of addition is generally about 10 ^-5 to 10 ^-2 mol per mol of silver halide. Known photographic additives which can be used for the light-sensitive material and the dye fixing material used in such a process are described in the above-mentioned RD Nos. 17, 643, 18 and 7.
No. 16 and Nos. 307 and 105,
The relevant locations are summarized in the table below.

Types of Additives RD17643 RD18716 RD307105 1. Chemical sensitizer page 23 page 648 right column page 866 2. Sensitivity increasing agent, page 648, right column 3. Spectral sensitizers, pages 23 to 24, page 648, right column 866 to 868, super sensitizers, page 649, right column 4. Optical brightener page 24 page 648 right column page 868 5. Antifoggant, pages 24 to 25, page 649, right column, pages 868 to 870, stabilizer. 6. Light absorbers, pages 25 to 26, page 649, right column, page 873, filter dyes, 頁 page 650, left column, ultraviolet absorbers. 7. Stain inhibitor 25 page right column 650 page left column to right column page 872 8. Dye image stabilizer page 25 page 650 left column page 872 10. Hardener page 26 page 651 left column pages 874-875 Binder page 26 page 651 left column pages 873 to 874 11. Plasticizers and lubricants page 27 page 650 right column page 876 12. Coating aid, pages 26 to 27, page 650, right column, pages 875 to 876 Surfactant 13. 13. Antistatic agent, page 27, page 650, right column, pages 876 to 877 Matting agent 878-879

As the binder for the constituent layers of the light-sensitive material, hydrophilic binders are preferably used. Examples thereof include the above-mentioned Research Disclosure and JP-A-64-13 / 1988.
No. 546, pages (71) to (75). Specifically, a transparent or translucent hydrophilic binder is preferable, and examples thereof include gelatin and gelatin derivatives. Gelatin may be selected from lime-processed gelatin, acid-processed gelatin, and so-called demineralized gelatin with a reduced content of calcium and the like according to various purposes.
It is also preferable to use them in combination.

As a method of exposing and recording an image on a photosensitive material, for example, a method of directly photographing a landscape or a person using a camera or the like, a method of exposing through a reversal film or a negative film using a printer or a enlarger, Scanning and exposing the original image through slits and the like using a copier exposure device, etc., light emitting diodes and various lasers (laser diodes,
A method of performing scanning exposure by emitting light from a gas laser or the like (JP-A-2-129625, JP-A-5-17614).
No. 4, No. 5-199372, No. 6-127022), image information is output to an image display device such as a CRT, a liquid crystal display, an electroluminescence display, a plasma display, etc., directly or through an optical system. Exposure method. As the light source for recording an image on the photosensitive material, natural light, a tungsten lamp, a light emitting diode, a laser light source,
US Patent No. 4,500,626 56
Column, JP-A-2-53,378 and JP-A-2-54,672 can be used. Also, image exposure can be performed using a wavelength conversion element in which a non-linear optical material and a coherent light source such as laser light are combined. Here, the non-linear optical material is a material that can exhibit nonlinearity between polarization and electric field that appears when a strong optical electric field such as laser light is applied, and lithium niobate,
Potassium dihydrogen phosphate (KDP), lithium iodate, B
Inorganic compounds represented by aB ₂ O _{4 and the} like, urea derivatives, nitroaniline derivatives, for example, nitropyridine-N-oxide derivatives such as 3-methyl-4-nitropyridine-N-oxide (POM); 61-5346
Compounds described in Nos. 2 and 62-210432 are preferably used. As a form of the wavelength conversion element, a single crystal optical waveguide type, a fiber type and the like are known, and any of them is useful. The image information includes an image signal obtained from a video camera, an electronic still camera, a television signal represented by the Nippon Television Signal Standards (NTSC), and an image obtained by dividing an original image into a number of pixels such as a scanner. An image signal generated using a computer represented by a signal, CG, or CAD can be used.

The method of developing the light-sensitive material containing the color developing agent of the present invention after exposure is as follows: an activator processing method of developing with an alkaline processing solution not containing a color developing agent; and an auxiliary developing agent / base. There is a method of processing with a processing solution containing, a method of developing the alkaline processing solution on a photosensitive material by a diffusion transfer method, and a method of processing by thermal development.

Activator processing refers to a processing method in which a color developing agent is incorporated in a light-sensitive material and is developed with a processing solution containing no color developing agent. In the present invention, the "activator liquid" is characterized in that it does not substantially contain a p-phenylenediamine-based color developing agent as conventionally used, and other components (eg, alkali, halogen, chelating agent, etc.) ) May be included. In some cases, it is preferable that a reducing agent is not contained in order to maintain processing stability. In this case, it is preferable that an auxiliary developing agent, hydroxyamines, sulfites, and the like are not substantially contained. Here, “substantially not contained” means preferably 0.5 mmol / l or less, more preferably 0.1 mmol / l or less. In particular, it is preferable not to contain at all. The pH of the alkaline treatment liquid is preferably from 9 to 14, and particularly preferably from 10 to 13. For the activator processing photosensitive material and its processing,
For example, Japanese Patent Application Nos. 7-63572 and 7-334190.
Nos. 7-334192, 7-334197 and 7-344396.

When the photosensitive material is developed using a developing solution in the present invention, the developing solution functions as a silver halide developing agent, and / or an oxidized developing agent generated in silver development contains an oxidized developing agent in the photosensitive material. A compound having a function of cross-oxidizing the color developing agent contained in the toner may be used. Preferred are pyrazolidones, dihydroxybenzenes, reductones and aminophenols, and particularly preferred are pyrazolidones. Other additives, processing formulas (methods), processing conditions, and the like used in the processing of development, bleaching, fixing, and washing (stabilization) are disclosed in
No. 101484, page 13, column 24, line 33 to page 19, 3
Those described in column 5, line 28 can be preferably applied. When the amount of silver halide used is small, the desilvering treatment can be omitted. The actual processing time in a developing machine using the processing liquid is usually determined by the linear velocity and the capacity of the processing bath. In the present invention, the standard of the linear velocity is 500 to 4000 mm / min. In particular, in the case of a small developing machine, the speed is preferably 500 to 2500 mm / min. The processing time from the entire processing step, that is, from the developing step to the drying step, is preferably 360 seconds or less, more preferably 120 seconds or less, and particularly preferably 90 to 30 seconds. Here, the processing time is the time from when the photosensitive material is immersed in the developing solution to when it comes out of the drying section of the processor.

The process of developing an alkaline processing solution by the diffusion transfer method is known in the art as an instant processing system, and includes at least one photosensitive layer / dye-forming layer (the photosensitive layer and the dye-forming layer are composed of the same layer). The photosensitive material having a mordant layer for capturing and mordanting the diffusible dye formed from the photosensitive layer / dye-forming layer on the same support or on a separate support is subjected to alkaline treatment. This means that the liquid is developed with a thickness of about 500 μm or less, preferably 50 to 200 μm. When an auxiliary developing agent is incorporated, it is preferable that the alkaline processing liquid does not contain the auxiliary developing agent for production and storage of the processing solution. In the case of the diffusion transfer method, the pH of the alkaline treatment liquid is preferably from 10 to 14, and particularly preferably from 12 to 14. See TH James, The Theory of Pho
4th edition of the tographic Process (1977, Macmillan)
The structure of a specific film unit is described in JP-A-63-226649. Examples of the materials included in the film unit and various layers including the same are described below. The dye receiving layer and the mordant contained therein are described in
No. 1-252551, U.S. Pat. No. 2,548,564.
No. 3,756,814, No. 4,124,38
No. 6, No. 3,625,694. For the neutralizing layer for lowering the pH of the photosensitive material after developing the alkaline processing solution, JP-B-7-122753,
U.S. Pat. No. 4,139,383, RD-No. 1610
The timing layer used in combination with the neutralizing layer is described in JP-A-54-136328.
No. 4,267,262, US Pat.
No. 9,030 and 4,268,604. Any emulsion can be used as the silver halide emulsion. Preferred auto-positive emulsions for photographic light-sensitive materials are JP-A-7-333770 and JP-A-7-33377.
No. 1 etc. can be given. In addition, if necessary, a light-shielding layer, a reflective layer, an intermediate layer, an isolation layer, an ultraviolet absorbing layer, a filter layer, an overcoat layer, an adhesion improving layer, and the like can be provided. The processing solution for processing the above-mentioned light-sensitive material contains processing components necessary for development, and usually contains a thickening agent and spreads uniformly on the light-sensitive material. Thickening agents such as carboxymethylcellulose and hydroxyethylcellulose are preferable as the thickener. Details of the photosensitive layer and the processing solution are described in
333371.

The heat treatment in the heat development of the light-sensitive material is known in the art and can be applied to the light-sensitive material of the present invention. The photothermographic material and its process are described, for example, in Photographic Industry Fundamentals (published by Corona in 1978).
53-555 pages, 40 pages of video information issued in April 1978,
Nebletts Handbook of Photography and Reprography,
7th Ed. (Van Nostrand and Reinhold Company) 3
Nos. 3,152,904, 3,301,678, 3,392,020, 3,457,075, British Patent 1,131,10
8, No. 1,167,777, and Research Disclosure Magazine, June 1978, pp. 9-15 (RD-
17029).

The light-sensitive material of the present invention is prepared in accordance with US Pat. No. 4,514,49 for the purpose of accelerating silver development and dye formation reaction.
Nos. 4,657,848 and 5 (published by Aztec Co., Ltd. on March 22, 1991), pages 55 to 86, etc. No. 660, U.S. Pat.
It is preferable to apply the base generation method described in No. 0,445. To the light-sensitive material of the present invention, a heat solvent described in U.S. Pat. Nos. 3,347,675 and 3,667,959 may be added for the purpose of accelerating thermal development. When the light-sensitive material of the present invention is subjected to heat treatment, in order to promote development and / or diffusion transfer of the processing material,
Water, an aqueous solution containing an inorganic alkali metal salt or an organic base,
It is also preferable to include a low-boiling solvent or a mixed solvent of a low-boiling solvent and water or the above-mentioned basic aqueous solution in a light-sensitive material or a processing sheet and heat-treat it. As a method using water, JP-A-63-144354 and JP-A-63-14 are known.
4,355, 62-38,460, JP-A-3-2
10,555, JP-A-62-253,159, and 6
3-85,544, EP 210,660 and U.S. Pat. No. 4,740,445. The present invention relates to JP-A-7-261336 and JP-A-7-26.
No. 8045, No. 8-30103, No. 8-46822, and No. 8-97344. The heating temperature in the thermal development step is about 50 ° C. to 200 ° C.
A temperature of 0 ° C. to 150 ° C. is useful, and when a solvent is used, it is preferably used at a temperature not higher than its boiling point.

[0110]

【Example】

(Example 1) <Method of preparing photosensitive silver halide emulsion> A well-stirred aqueous gelatin solution (inert gelatin 3 in 1000 ml of water)
0 g, potassium bromide 2 g) and ammonia
Add ammonium nitrate as a solvent and keep the temperature at 75 ° C.
To this, 1,000 ml of an aqueous solution containing 1 mol of silver nitrate and 1000 ml of an aqueous solution containing 1 mol of potassium bromide and 0.03 mol of potassium iodide were simultaneously added over 78 minutes. After washing with water and desalting, the mixture was redispersed by adding inert gelatin to obtain a sphere equivalent diameter of 0.1.
A silver iodobromide emulsion having an iodine content of 3 .mu.% Of 76 .mu.m was prepared. The ball equivalent diameter is a model TA from Coulter Counter
Measured at -II. Potassium thiocyanate, chloroauric acid, and sodium thiosulfate were added to the above emulsion at 56 ° C. for optimal chemical sensitization. Sensitizing dyes corresponding to the respective spectral sensitivities were added to the emulsion at the time of preparing the coating solution to give color sensitivity.

<Method for Preparing Zinc Hydroxide Dispersion> 31 g of zinc hydroxide powder having a primary particle size of 0.2 μm,
1.6 g of carboxymethylcellulose, 0.4 g of sodium polyacrylate, 8.5 g of lime-treated ossein gelatin, and 158.5 ml of water were mixed as a dispersant, and the mixture was dispersed in a mill using glass beads for 1 hour. After the dispersion, the glass beads were filtered off, and a dispersion 188 of zinc hydroxide was obtained.
g was obtained.

<Method for Preparing Emulsified Dispersion of Coupler> Table 1
The oil phase component and the water phase component having the compositions shown in
Make a homogeneous solution at 0 ° C. The oil phase component and the water phase component were combined, and in a 1-liter stainless steel container, a dissolver with a disperser having a diameter of 5 cm provided a 10,000 rp.
m for 20 minutes. To this, warm water in the amount shown in Table 1 was added as post-water and mixed at 2000 rpm for 10 minutes. Thus, an emulsified dispersion of couplers of three colors of cyan, magenta and yellow was prepared.

[0113]

[Table 1]

[0114]

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[0115]

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Using the thus obtained materials, heat-developable color light-sensitive materials 101 having a multilayer structure shown in Tables 2 and 3 were produced.

[0117]

[Table 2]

[0118]

[Table 3]

[0119]

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[0120]

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[0121]

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Further, a processing material R-1 having the contents shown in Tables 4, 5, and 6 was prepared.

[0123]

[Table 4]

[0124]

[Table 5]

[0125]

[Table 6]

[0126]

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[0127]

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Next, as shown in Table 7, photosensitive materials 102 to 112 having exactly the same composition as 101 except that the coupler and the developing agent were changed were prepared. The photosensitive materials 101 to 112 thus formed are passed through a B, G, or R filter having a continuously changed density to 2500 lu.
Exposure for 0.01 second at x. 40 ° C on the exposed photosensitive material surface
Hot water was applied at 15 ml / m ^2, and the treated sheet and each other were superposed on each other.
Heat development was performed for 0 seconds. When the image receiving material was peeled off after the processing, clear color images of cyan, magenta and yellow were obtained corresponding to the filters exposed on the light-sensitive material side. Immediately after the processing, the maximum density part (Dmax) and the minimum density part (Dmin) of the yellow dye image of the B exposure part, the magenta image of the G exposure part, and the cyan image of the R exposure part of this sample were measured with an X-rite densitometer. Table 8 shows the measurement results.

[0129]

[Table 7]

[0130]

[Table 8]

From the results shown in Table 8, it can be seen that the present invention can effectively lower the minimum density without substantially lowering the maximum density. Also, the single colors of yellow, magenta, and cyan did not have a haze and developed a clear color. From the above results, the effect of the present invention is clear.

(Example 2) After a corona discharge treatment was applied to the surface of a paper support laminated on both sides with polyethylene,
Providing a gelatin subbing layer containing sodium dodecylbenzenesulfonate, and further coating various photographic constituent layers,
A multilayer color photographic paper (201) having the following layer configuration was produced. The coating solution was prepared as follows. First layer coating solution 22.3 g of yellow coupler (EXY-1), 12.3 g of color developing agent (EXCD-1), solvent (Solv-
1) 80 g was dissolved in ethyl acetate, and this solution was emulsified and dispersed in a 16% gelatin solution containing 10% sodium dodecylbenzenesulfonate and citric acid to prepare an emulsified dispersion A. On the other hand, silver chlorobromide emulsion A (cubic, large-sized emulsion A having an average grain size of 0.88 μm and 0.70 μm
3: 7 mixture with small-sized emulsion A (silver molar ratio)). The coefficient of variation of the particle size distribution was 0.08 and 0.1, respectively.
0, in each size emulsion, 0.3 mol% of silver bromide was locally contained on a part of the surface of the grain having silver chloride as a base material). This emulsion contains blue-sensitive sensitizing dyes A, B, and C shown below.
Is 1.4 × 10 ⁻⁴ mol for large-size emulsion A per mol of silver, and
1.7 × 10 ^-4 mol was added in each case. The emulsion was chemically ripened by adding a sulfur sensitizer and a gold sensitizer. The emulsified dispersion A and the silver chlorobromide emulsion A were mixed and dissolved to prepare a first layer coating solution having the following composition. The emulsion coating amount indicates a silver equivalent coating amount.

[0133]

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The coating solutions for the second to seventh layers were prepared in the same manner as the coating solution for the first layer. As a gelatin hardener for each layer, 1-oxy-3,5-dichloro-s-triazine sodium salt was used. In addition, Cpd-2, Cpd
-3, Cpd-4 and Cpd-5 each having a total amount of 1
^{5.0mg / m 2, 60.0mg / m} 2, was added to a 50.0 mg / m ² and 10.0 mg / m ^2. The following spectral sensitizing dyes were used for the silver chlorobromide emulsion in each photosensitive emulsion layer. (Blue-sensitive emulsion layer)

[0135]

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[0136]

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[0137]

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(Per mol of silver halide, 1.4 × 10 ^-4 mol was added for large-size emulsions, and 1.7 × 10 ^-4 mol was added for small-size emulsions.) Green-sensitive emulsion layer)

[0139]

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(The sensitizing dye D was used in an amount of 3.0 × 10 ^-4 mol for a large-size emulsion, 3.6 × 10 ^-4 mol for a small-size emulsion, and Sensitizing dye E was used in an amount of 4.0 × 10 ^-5 mol per mol of silver halide and 7.0 mol per mol of silver halide.
× 10 ^-5 mol, and 2.0 × 10 ^-4 mol of sensitizing dye F per mol of silver halide per mol of silver halide and 2.8 × 10 ^-4 mol per mol of silver emulsion. Was added. ) (Red-sensitive emulsion layer)

[0141]

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(5.0 × 10 ⁻⁵ mol was added per mol of silver halide to the large-size emulsion and 8.0 × 10 ⁻⁵ mol was added to the small-size emulsion). The following compounds were used per mole of silver halide.
6 × 10 ^-2 mol was added.

[0143]

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Further, 1- (5-methylureidophenyl) was added to the blue-sensitive emulsion layer, green-sensitive emulsion layer and red-sensitive emulsion layer.
-5-mercaptotetrazole was used in an amount of 3.5 × 10 ^-4 mole, 3.0 × 10 ^-3 mole, 2.5
× 10 ^-4 mol was added. Further, 4-hydroxy-6-methyl-1,3,3 was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer.
a, 7-Tetrazaindene was added in an amount of 1 × 10 ⁻⁴ mol and 2 × 10 ⁻⁴ mol per mol of silver halide, respectively.
To prevent irradiation, the following dyes were added to the emulsion layer (the values in parentheses indicate the coating amount).

[0145]

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(Layer Structure) The composition of each layer is shown below. The numbers represent the coating amount (g / m ² ). The silver halide emulsion represents a coating amount in terms of silver. 2. Support Polyethylene laminated paper [The first layer side polyethylene contains white pigment (TiO ₂ ) and blue dye (ultra blue)] First layer (blue-sensitive emulsion layer) Silver chloride emulsion A 0.40 gelatin 00 Yellow coupler (EXY-1) 0.41 Color developing agent (EXCD-1) 0.27 Solvent (Solv-1) 1.50

Second layer (color mixture preventing layer) Gelatin 1.09 Color mixture inhibitor (Cpd-6) 0.11 Solvent (Solv-1) 0.19 Solvent (Solv-3) 0.07 Solvent (Solv-4) 0.25 Solvent (Solv-5) 0.09 Third layer (green-sensitive emulsion layer) Silver chlorobromide emulsion: Cubic, large-size emulsion B having an average grain size of 0.55 μm; 1: 3 mixture with 39 μm small size emulsion B (silver molar ratio). The coefficient of variation of the grain size distribution was 0.10 and 0.08, respectively, and in each size emulsion, 0.8 mol% of AgBr was locally contained on a part of the grain surface based on silver chloride. 0.20 Gelatin 1.50 Magenta coupler (EXM-1) 0.20 Color developing agent (EXCD-1) 0.13 Solvent (Solv-2) 0.67

Fourth Layer (Color Mixing Prevention Layer) Gelatin 0.77 Color Mixture Prevention Agent (Cpd-6) 0.08 Solvent (Solv-1) 0.14 Solvent (Solv-3) 0.05 Solvent (Solv-4) 0.14 Solvent (Solv-5) 0.06 Fifth layer (red-sensitive emulsion layer) Silver chlorobromide emulsion: Cubic, large-size emulsion C having an average grain size of 0.5 μm; 1: 4 mixture with small size emulsion C of 41 μm (silver molar ratio). The coefficient of variation of the grain size distribution was 0.09 and 0.11, and in each emulsion, 0.8 mol% of AgBr was locally contained in a part of the grain surface based on silver chloride. 15 Cyan coupler (EXC-1) 0.22 Color developing agent (EXCD-2) 0.16 Solvent (Solv-1) 0.18

Sixth layer (ultraviolet absorbing layer) Gelatin 0.64 Ultraviolet absorbing agent (UV-1) 0.39 Color image stabilizer (Cpd-7) 0.05 Solvent (Solv-6) 0.05 Seventh layer (Protective layer) Gelatin 1.01 Acrylic modified copolymer of polyvinyl alcohol (degree of modification 17%) 0.04 Liquid paraffin 0.02 Surfactant (Cpd-1) 0.01

[0150]

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[0151]

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[0152]

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To the sample (201), except that the coupler and the color developing agent were replaced in equimolar amounts by the color developing coupler and the color developing agent shown in Table 9, and the active site-unsubstituted coupler was added in the ratio shown in the table. Samples (202) to (209) were produced in exactly the same manner as the production of the sample (201).

[0154]

[Table 9]

For all the samples prepared as described above, the gradation exposure of a three-color separation filter for sensitometry was performed using a FWH type photometer (color temperature of light source: 3200 ° K) manufactured by Fuji Film Co., Ltd. Gave.

The samples after exposure were processed in the following processing steps using the following processing solutions. Processing Step Temperature Time Current image 40 ° C 15 seconds Bleaching and fixing 40 ° C 45 seconds Rinse room temperature 45 seconds Alkaline processing room temperature 30 seconds (developer) Water 800 ml Potassium phosphate 40 g Disodium-N, N-bis (sulfonate) Ethyl) hydroxylamine 10 g KCl 5 g hydroxyethylidene-1,1-disulfonic acid (30%) 4 ml 1-phenyl-4-methyl-4-hydroxymethyl-3-pyrazolidone 1 g Water was added to add 1000 ml pH (25 ° C./hydroxylation) 12.0 with potassium)

(Bleaching-fixing solution) Water 600 ml Ammonium thiosulfate (700 g / l) 93 ml Ammonium sulfite 40 ml Ammonium iron (III) ethylenediaminetetraacetate 55 g Ethylenediaminetetraacetic acid 2 g Nitric acid (67%) 30 g 5.8 (rinse solution) 5.8 (rinse solution) Chlorinated sodium isocyanurate 0.02 g Deionized water (conductivity 5 μS / cm or less) 1000 ml pH 6.5 (alkaline treatment solution) 0.1 N sodium hydroxide The maximum color density of the processed sample is indicated by red light, green light,
It was measured with blue light. Table 10 shows the results.

[0158]

[Table 10]

As is clear from the results shown in Table 10, it is understood that the light-sensitive material of the present invention lowers the minimum density without substantially impairing the maximum density. Further, the single colors of yellow, magenta and cyan were also reproduced more vividly than the comparative example. From the above results, the effectiveness of the present invention is clear.

[0160]

According to the present invention, the minimum density (fog) can be reduced without substantially impairing the maximum density of the dye image.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location G03C 8/40 505 G03C 8/40 505

Claims (3)

[Claims] 1. A dye which undergoes a coupling reaction with a color developing agent represented by the following general formula (I) and an oxidized form of the color developing agent in at least one hydrophilic colloid layer provided on a support. A color-forming coupler for forming an image, and further comprising a coupler which undergoes a coupling reaction with an oxidized form of the color-developing agent but does not cause color development to the extent that it substantially contributes to image density. Silver halide photographic material. Embedded image In the general formula (I), Z represents a carbamoyl group, an acyl group, an alkoxycarbonyl group, or an aryloxycarbonyl group, and Q represents an atomic group forming an unsaturated ring together with C. 2. An image forming method comprising thermally developing the silver halide photographic material according to claim 1. 3. An image forming method comprising developing the silver halide photographic material according to claim 1 in a solution.